JPH0339954A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To accelerate desilvering by forming a hydrophilic colloidal layer contg. dispersed microcrystals of a specified compd. and incorporating a specified bleaching accelerator releasing compd. CONSTITUTION:A hydrophilic colloidal layer contg. dispersed microcrystals of a compd. represented by formula I, etc., is formed and a bleaching accelerator releasing compd. represented by formula II is incorporated. In the formula I, A is an acidic nucleus having carboxyphenyl, etc., R is H or alkyl, each of R1 and R2 is alkyl, acyl, etc., each of R3 and R6 is H, hydroxy, etc., and each of R4 and R5 is H or a group of atoms required to form a 5- or 6-mem bered ring by the combination of R1 with R4 or R2 with R5. In the formula II, A is a group whose bond to (T1)l is cleaved by reaction by a reaction with the oxidized product of a developing agent, each of T1 and T2 is a timing group, B is a group whose bond to (T2)n is cleaved by a reaction with the oxidized product after the bond to (T1)l is cleaved, Z is a group which exhibits bleaching accelerating action after the bond to (B-(T2)n)m is cleaved and each of l, m and n is 0 or 1. Desilvering speed can be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved desilvering properties.

(Prior Art) Silver halide color photographic materials are generally processed through a color development step and a delineation step after being exposed to light. There is a strong need to shorten the required time, and in particular, shortening the desilvering process, which accounts for nearly half of the processing time, is a major issue.

Hitherto, methods have been proposed in which various bleach accelerators are added to bleach baths, bleach-fix baths, or their pre-baths as a method of increasing the bleaching strength to speed up the desilvering process. Although such bleaching accelerators are described in Japanese Patent Application No. 8445/1983, they have not yet reached a satisfactory level in terms of stability and effectiveness in bleaching baths.

``Although a method in which these compounds are present in a photographic material is also known, this method also has many problems, including the fact that it has a large undesirable effect on photographic performance.

In contrast, Research Disclosure NcL24
No. 241, No. 11449, and JP-A-61-2012
No. 47 describes a bleach accelerator releasing coupler. The use of these compounds increases the derailment speed, but there are certain limits, and even if these compounds are used, it is still insufficient in terms of shortening the desilvering process, and the development of a method to further shorten the process is strongly desired. was. When using a bleach-fixing bath that performs bleaching and fixing in one bath, which emphasizes the simplicity of the processing process, the bleaching blade becomes weaker, so there has been a particular demand for shorter processing times.

On the other hand, in silver halide photographic materials, it is well known to provide a light absorption filter, a layer that absorbs light of a specific wavelength for the purpose of preventing halation or adjusting sensitivity. Setting the yellow filter layer at a position closer to the support and farther from the support than the other color-sensitive layers is a method of cutting the inherent sensitivity of the green and red light-sensitive emulsions, or placing an unnecessary yellow filter layer on the side closer to the support than the light-sensitive emulsion layers. The method of providing an antihaleshitane layer to prevent light scattering is currently the most commonly used method. From a practical standpoint, fine particles of colloidal silver are usually used in these light absorption layers. However, these colloidal silver particles are known to cause deleterious contact fog to adjacent emulsion layers and reduce desilvering rates. In order to prevent these contact fogs, Japanese Patent Application Laid-Open No. 62-32460 and Japanese Patent Application No. 63-
It was necessary to add an antifoggant as described in No. 44159. It is stated in the above patent that addition of these inhibitors not only reduces the sensitivity but also greatly reduces the desilvering rate.

(Secret B to be Solved by the Invention) In order to improve this point, attempts have been made to use organic dyes in the filter layer instead of colloidal silver, as described in the above-mentioned patents and the like. When these dyes are used, the desilvering speed increases to some extent, but they have poor decolorizing properties in the processing solution and unnecessary absorption remains after processing, resulting in an increase in Dmtn.
There are side effects such as insufficient fixation of the dye to a specific layer and diffusion to multiple layers during storage, resulting in fluctuations in photographic properties. Many efforts have been made to obtain satisfactory dyes.

For example, US Pat. No. 2,548,564 discloses a method in which a dissociated anionic dye and a hydrophilic polymer having an opposite charge are co-existed together as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. 4,124,386
No. 3,625°694, etc.

Furthermore, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-155350.
No. 88-155351, No. 63-27838,
No. 63-197943, European Patent No. 15,601,
274,723, 276.566, 299,
No. 435, International Patent No. 88104794, etc.

By using the dyes described in these publications, it has become possible to improve the derailment speed without adversely affecting photographic properties, but the level of derailment speed is still not sufficient, and a method that can further shorten the time has been desired.

Therefore, the first object of the present invention is to provide a silver halide color photographic material that can speed up the delineation process. The second object is to provide a color photographic material that has excellent decolorizing properties and has a quick delineation process. The third object is to provide a silver halide color photographic material with improved desilvering speed when using a bleach-fix bath.

(Means for Solving the Problems) As a result of intensive research, the present inventors found that the object of the present invention can be achieved by the following means.

That is, the present invention provides a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the light-sensitive material contains at least one compound selected from the following general formulas (I) to (V). a hydrophilic colloid layer containing a microcrystalline dispersion, and at least one layer has the following general formula (Y
) The present invention relates to a silver halide color photographic light-sensitive material containing at least one bleach accelerator-releasing compound shown in (a).

General formula (I) General formula (n) General formula (I [[) % formula % General formula (■) A+L+-Lz? i--8 General formula (V) (In the formula, A and A' may be the same or different, and carboxyphenyl group, sulfamoylphenyl group, and sulfona are substituted with dophenyl group, carboxyalkyl group, and hydroxyphenyl group) Or it represents an unsubstituted acidic nucleus, and examples of the acidic nucleus include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbic acid, thiobarbic acid, indandione, pyrazolo Selected from the group consisting of pyridine and hydroxypyridone.B
represents a substituted or unsubstituted basic nucleus having a carboxyl group, sulfamoyl group or sulfonamide group, and the basic nucleus is selected from the group consisting of pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole and pyrrole. It will be done. R represents a hydrogen atom or an alkyl group, R, and R each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group, or a sulfonyl group;
, may be linked to form a 5- or 6-membered ring, R3, R
4 represents a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, or a halogen atom;
R, are each a hydrogen atom, Ro and R4, or R2 and R3
Represents a group of nonmetallic atoms necessary for linking together to form a 5- or 6-membered ring.

L+, Lt, and Lz each represent a substituted or unsubstituted methine group, X and Y each represent an electron-withdrawing group, and X, Y
at least one carboxyphenyl group, sulfamoylphenyl group, sulfonamidophenyl group,
Having a carboxyalkyl group or a hydroxyphenyl group, 0m represents 0 or l, n represents 02 l or 2, p represents 0 or l, but when P is O, R1 represents a hydroxyl group or a carboxy group, and R4 and R2 represent hydrogen atoms,) General formula (Y) A-(T,)j -CB-('rz)+t,), -
Z In the above formula, A represents a group whose bond with (TI)J or less is cleaved upon reaction with the oxidized product of an aromatic primary amine developer;
1 and T are tie arsenal groups, and B is (T,) * After the bonds with the above are cleaved, the bonds with the following are cleaved by reaction with the oxidized product of the aromatic primary amine developer. The group to be cleaved is Z
is (B-(Tri,).

A group that exhibits a bleaching promoting effect after the bond with the above is cleaved,
l, m and n represent an integer of O or 1.

Then - formulas (I), (II) (DI), (TV)
and each group in (V) will be explained in detail.

The carboxyphenyl group possessed by the acidic nucleus represented by A or A' and the electron-withdrawing group represented by X or Y includes not only one but also a phenyl group having two or three carboxy groups; , sulf-1-moylphenyl, sulfonamidophenyl, and hydroxyphenyl groups also include phenyl groups having not only one but also two or three sulfamoyl, sulfonamido, and hydroxy groups, respectively; , substituents other than sulfonamide groups and hydroxy groups (substituents include pK in a solution with a volume ratio of water and ethanol of 1:1)
There is no particular restriction as long as a (acid dissociation constant) is a dissociative substituent or a non-dissociative substituent of 4 or more.Specifically, 4-carboxyphenyl, 3. 5-dicarboxyphenyl, 2,4-dicarboxyphenyl,
3-carboxyphenyl, 2-methyl-3-carboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2.5-dicarboxyphenyl, 2.4.6-doli Hydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p-cyanobenzenesulfonamido)phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2,4-dihydroxyphenyl, 3.4.5 -) dihydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4
-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, etc., and these groups can be bonded not only directly to the acidic nucleus but also via a methylene group, ethylene group or propylene group. Also good.

The acidic nucleus represented by A, A' and the electron-withdrawing group represented by X or Y each have a carboxyalkyl group of 1 to 10
Carbon atoms are preferred, such as carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-carboxypropyl, 4-carboxybutyl,
Groups such as 8-carboxyoctyl can be mentioned.

The alkyl group represented by R, R, or Rh has 1 to 1 carbon atoms.
10 alkyl groups are preferred, such as methyl, ethyl,
Mention may be made of groups such as n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R,, R, is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl,
n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred; , ethoxy), alkoxycarbonyl groups (e.g.
methoxycarbonyl, i-propoxycarbonyl) aryloxy group (e.g. phenoxy group), phenyl group,
It may have an amide group (eg, acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), or a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl).

The aryl group represented by R+ and Rt is preferably a phenyl group or a naphthyl group, and the substituents include the above R1
The substituents of the alkyl group represented by and Rt include the groups and alkyl groups (eg, methyl, ethyl). ].

The acyl group represented by RISRt is preferably an acyl group having 2 to 10 carbon atoms, such as acetyl, propionyl,
n-octanoyl, n-decanoyl, isobutanoyl,
Mention may be made of groups such as benzoyl - R+ , R
The alkyl or arylsulfonyl group represented by z includes methanesulfonyl, ethanesulfonyl, n-
Examples include groups such as methanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-)luenesulfonyl, and 0-carboxybenzenesulfonyl.

The alkoxy group represented by R,, R, has 1 to 10 carbon atoms.
Preferred are alkoxy groups such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, and impropoxy.The halogen atoms represented by R2 and R4 include chlorine, bromine, etc. , fluorine.

Examples of the ring formed by linking R1 and R4 or R1 and R include a julolidine ring.

Examples of the 5- or 6-membered ring formed by linking R and Rt include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L, , L, , L may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X and Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-lyloroheptyl group, etc.), arylcarbonyl group (arylcarbonyl group that may be substituted, such as benzoyl, 4
-ethoxycarbonylbenzoyl, 3-chlorobenzoyl group), alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2
-Ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, oftadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2 -(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)
ethoxy] ethoxycarbonyl group), aryloxycarbonyl group (aryloxycarbonyl group that may be substituted, such as phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxy carbonyl, 4-methoxyphenoxycarbonyl, 2,4-di(t-amol)phenoxycarbonyl group), carbamoyl group (a carbamoyl group that may be substituted with R, such as carbamoyl, ethylcarbamoyl,
Dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4 -hexyloxyphenylcarbamoyl, 2,4-di(I
-amyl) phenylcarbamoyl, 2-chloro-3-(
dodecyloxycarbonyl) phenylcarbamoyl, 3
-(hexyloxycarbonyl)phenylcarbamoyl), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl group, etc.), and a sulfamoyl group (a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

-1 -2 -3 -4 -5 [-6 -7 ! -8 ! -9 ! -11 ■-12 ■-13 ■-14 -15 ■-16 ■-17 ■-18 -19 ! -20 -21 ■-22 ! -25 ■-26 ! -27 ■-28 [[-1 -2 -3 f-4 ! 1-5 I-6 I[[-1 -2 -3 ■-5 111-6 1[[-7 ■-8 I[1-9 ll-10 ■-11 -12 ■-13 Coo)I OOH lll-14 ■-15 +11-16 ■-17 ■-18 1[[-19 11[-20 ■-21 ■-22 ■-23 ■-24 ■-25 ■-26 Cool ■-28 ■-29 C.B.

H3 If-31 Coco.

■-32 -33 Hs 0CHs Hs 111-34 ■-35 ■-1 C,ll.

V-2 C*Hs V-4 V-5 tHs V-7 Js V-8 V-9 rv-t.

C,U.

■-12 ■-14 F/-15 V-16 Js -1 -2 -3 Cl Co-4 COOH・ -5 -6 V-7 The dye used in the present invention is based on international patent WO3810479.
No. 4, European Patent EPO 274723A, 27
No. 6.566, No. 299.435, JP-A-52-92
No. 716, No. 55-155350, No. 55-1553
No. 51, No. 61-205934, No. 4 B-6862
No. 3, U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897
No. 3746539, No. 3933798, No. 41
30429, No. 4040841, etc., and the bottom can be easily formed according to the method.

In the present invention, the dye is formed into a solid fine powder dispersion for inclusion in a layer, such as a hydrophilic colloid layer, coated on a photographic element. The fine powder dispersion can be prepared by precipitating the dye in the form of a dispersion and/or in the presence of a dispersant by known micronization means, such as ball milling (ball mill, vibrating ball mill, planetary ball mill, etc.), side milling. , can be formed by colloid milling, jet milling, roller milling, etc., in which case a solvent (
For example, water, alcohol, etc.) may coexist.

Alternatively, after dissolving the dye in a suitable solvent, a non-solvent for the dye may be added to precipitate a microcrystalline powder of the dye, in which case a dispersing surfactant may be used.

Alternatively, the dye may be pH controlled so that it is first dissolved and then crystallized by changing the pH.

The dye particles in the dispersion have an average particle diameter of 10 μm or less, preferably 2 μm or less, and particularly preferably 0.5 μm.
or less, and in some cases 0. More preferably, it is a fine powder of 1 μm or less.

The amount of dye used in the present invention is 1~1000/
Used in the range of Preferably 5~800mg/
It is rrr.

The dye dispersion of the present invention can be added to any layer, regardless of whether it is an emulsion layer or an intermediate layer.

However, the yellow filter layer and/or antihalesia a
The effects of the present invention are remarkable when a part or all of the colloids commonly used in the coating layer are used as substitutes.

The bleach accelerator releasing compound (hereinafter referred to as a BAR compound) used in the present invention is represented by the formula (Y).

General formula (Y) A - (Y 1) J - (B (T z), ), -Z
- In the formula (Y), A is a group that can cleave the bond with (TI)J or less by reaction with the oxidized product of an aromatic primary amine developer, T1 and T2 are timing groups, and B is ( T
, ) ), a group exhibiting a bleaching promoting effect after the bond with the above is cleaved, i,
and n represents an integer of 0 or 1.

In general formula (Y), A specifically represents a coupler residue or a reducing agent residue.

As the coupler residue represented by A, known ones can be used. For example, yellow coupler residue (for example, open-chain ketomethylene type coupler), magenta coupler residue (for example, 5-
cyan coupler residues (eg, phenol type, naphthol type couplers), and colorless coupler residues (eg, indanone type, acetonephenone type couplers). Also, European Patent No. 249453
No. 4,315,070, U.S. Pat. No. 4,183.
No. 752, No. 3,961,959 or No. 4,171
, 223.

When A represents a coupler residue in general formula (Y), A
Preferred examples are the following formulas (Cp-1), (Cp-2)
, (Cp-3), (Cp-4), (Cp-5), (C
p-6), (Cp-7), (Cp-8), (Cp-9
) or (Cp-10). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-3') General formula (Cp-4) General formula (Cp-5) General formula (Cp-6) H General formula (Cp-7 ) H General formula (Cp-8) H General formula (Cp-9) General formula (CP-10) H In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group .

In the above formula, RS l s RS ! , R53, Rsa
,Rss,R8&,Rat,Ro,R%! , R60, R
When h l s Rk 1 or R63 contains a diffusion-resistant group, it has a total number of carbon atoms of 8 to 40, preferably l
O to 30; otherwise,
In the case of a bis-type, telomer-type or polymer-type coupler in which the total number of carbon atoms is preferably 15 or less, any of the above substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon numbers may be outside the specified range.

R5I to Rh3, d and e will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group, or a heterocyclic group, R4, represents an aromatic group or a heterocyclic group, and R42, R44, and R6 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. represents a group.

R5I has the same meaning as R□ *Rsz and R33
each has the same meaning as R4□, R34 is R1Ra+
5Ot N- group, R,, S- group, Ro〇- group, 8 R%% represents a group with the same meaning as R41 aR1 & and Rst each represent a group with the same meaning as R41 group, R,, S- group,
Ro〇- group, R4, C0N- group, R4! or R4, SCh N-group *R8I is R41
and 43 5R89, which represents a group with the same meaning, is R with the same meaning as R41.
represents an arO- group, an R41S- group, a halogen atom, or an R□N- group; d represents 0 to 3;

When R1 d is plural, the plural R59s represent the same substituent or different substituents, or each R39 may become a divalent group and connect to form a cyclic structure.

Typical examples of divalent groups for forming a cyclic structure include: Here, [ is an integer from 0 to 4,
g represents an integer from 0 to 2, each representing 4, R4° is R4,
R41 represents a group with the same meaning as R4□, Rhz represents a group with the same meaning as Ro, R□C0NH- group, R,l0CONH- group, R41SOz NH- group, R4
30- group, R,, S- group, halogen atom or R,, N
-5, R1 is a group having the same meaning as Rat, [ 43 R41SOz - group, R430C〇- group, R-so-3
ow- group, halogen atom, nitro group, cyano group or R
, , represents a CO- group, e represents an integer from 0 to 4, and when there is a plurality of RhZ or Rh3, each represents the same or different.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.

The aromatic group is preferably a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably a 3- to 8-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, R,, O- group, R4&S- group, R,, NSO20 group, Examples thereof include aiSOi - group, R,, OSO, - group, cyano group, and nitro group. Here, R44 represents an aliphatic group, an aromatic group, or a heterocyclic group, and Raq, R41, and R4Q each represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. or heterocyclic group has the same meaning as defined above.

-8 Coupler residues represented by formula (Cp-1) are disclosed in, for example, U.S. Pat. Nos. 3,933,501 and 4.022,6
No. 20, No. 4,326.024, No. 4,401,
No. 752, Special Publication No. 58-10739, British Patent No. 1,
No. 425.020, No. 1,476.760, No. 2
It is specifically described in No. 49,473, etc.

The coupler residue represented by the general formula (Cp-2) is disclosed in, for example, US Pat. No. 4,149,886, British Patent No. 1,204
, No. 680, JP-A-52-154631, etc.

- The coupler residue represented by formula (Cp-3) is, for example, JP-A-49-111631, JP-A-54-48540,
No. 55-62454, No. 55-118034, No. 5
No. 6-38045, No. 56-80045, No. 56-1
No. 26833, No. 57-4044, No. 57-3585
No. 8, No. 57-94752, No. 58-17440,
No. 58-50537, No. 5 B-85432, No. 5
No. 8-117546, No. 5B-126530, No. 58
No.-145944, No. 5B-205151, JP-A-5
No. 4-170, No. 54-10491, No. 54-212
No. 58, No. 53-46452, No. 53-46453, No. 57-36577, Japanese Patent Application No. 58-110596, No. 58-132134, No. 59-26729, U.S. Patent No. 3,227.554, Same No. 3,432,521
No. 4,310,618, No. 4,351,89
It is specifically described in No. 7, etc.

- Coupler residues represented by formulas (Cp-4) and (Cp-5) are, for example, International Patent Nos. 3,705,8
No. 96, No. 3,725.067, No. 4,500.63
No. 0, No. 4゜540.654, No. 4,548,899
No. 4.581,326, No. 4.607,002, No. 4,621,046, No. 4,675,280,
JP-A-59-228252, JP-A No. 60-33552,
No. 60-43659, No. 60-55343, No. 60
No. -57838, No. 60-98434, No. 60-. 1
No. 07032, No. 61-53644, No. 61-652
No. 43, No. 61-65245, No. 61-65246, No. 61-65247, No. 61-120146, No. 61-120147, No. 61-120148, No. 6
No. 1-120149, No. 61-120150, No. 61
-120151, 61-120152, 61-
No. 120153, No. 61-120154, No. 61-1
No. 41446, No. 61-144647, No. 61-14
No. 7254, No. 61-151648, No. 61-180
No. 243, No. 61-228444, No. 61-2301
No. 46, No. 61-230147, No. 61-29214
It is specifically stated in No. 3, etc.

General formulas (Cp-6), (Cp-7) and (Cp-8)
For example, the coupler residue represented by
, No. 212, No. 4.146.396, No. 4,22
No. 8,233, No. 4,296,200, No. 2 and 3
No. 69.929, No. 2.801,171, No. 2.
No. 772,162, No. 2,895.826, No. 3
, 772゜002, 3,758.308, 4゜334.011, 4,327,173, West German Patent No. 3,329.729, European Patent No. 121.3
65A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,
No. 333,999, No. 4,451.559, No. 4
．． European Patent No. 427.767, European Patent No. 4.554,244, European Patent No. 161.626A, European Patent No. 175,573, European Patent No. 2
It is specifically described in No. 50,201 and the like.

The coupler residue represented by the general formula (Cp-9) is disclosed in, for example, U.S. Pat. Nos. 3,932,185 and 4.063,9
It is specifically described in No. 50 etc.

The coupler residue represented by the general formula (Cp-10) is specifically described in, for example, US Pat. No. 4,429,035.

A typical example of the coupler residue represented by the formula (Cp-1) is the compound example (Y-
1) to (Y-34) and similarly represented by the general formula (Cp-3), the coupler residues represented by the general formula (Cp-3) are expressed by the compound examples (M-1) to (M-56).
-4) and (Cp-5), according to compound examples (M-57) to (M-108),
- For coupler residues represented by formulas (Cp-6) and (Cp-7), compound examples (C-1) to (C-56)
Typical examples of the coupler residue represented by the formula (Cp-8) are described in Compound Examples (C-57) to (C-86).

The compound represented by the general formula (Y) may be a dimeric or polymeric compound that is bonded to each other at a portion other than Z (preferably A), and specific examples thereof can be found in, for example, Japanese Patent Application No. 62-90442. Are listed.

As the reducing agent residue represented by A, for example, Japanese Patent Application No. 62-2
No. 03997, page 78 - from formula (It) to page 85 -
The reducing agent residue represented by the formula (IV) (for example, a residue having a structure of a derivative such as hydroquinone, naphthohydroquinone, catechol, pyrogallol, aminophenol, gallic acid, etc.) is -Funetsuri.

In the general formula (Y), the timing groups represented by T1 and T2 are used for various purposes (for example, coupling activity il1
section) as appropriate. As examples of these timing groups, there are those shown in items (I) to (5) and (7) from pages 23 to 36 of Japanese Patent Application No. 186939/1982, and among these, the general formula (T-1), (T-2
) and (T-3) are preferred.

The group represented by B in the -S formula ("l') is (TI)
After separation from one or more groups, ie TI or A, it functions as a coupler or reducing agent (e.g. derivatives of hydroquinone, naphthohydroquinone, catechol, pyrogallol, aminophenol, gallic acid, etc.) and converts T3 by a coupling reaction or redox reaction. Represents a group that releases:

For example, US Pat. No. 4,438,193, US Pat. No. 4,618,57
No. 1, JP-A-60-203943, JP-A No. 60-2139
No. 44 and No. 61-236551, etc., and specific examples include the following groups.

/ 0 (CHs) tNsO* 〇-Here, * is the bonding position with T, and *ne is T! represents the bonding position with each.

T, , T, and B are used as appropriate depending on the purpose.

-i In formula (Y), the group represented by Z is specifically a known bleach accelerator residue. For example, U.S. Pat.
893.858, British Patent No. 1138842, various mercapto compounds described in JP-A-53-141623, compounds having disulfide bonds as described in JP-A-53-95630, and JP-B-Sho 53-9854. thiazolidine derivatives of The dithiocarbamate salts described in JP-A No. 55-26506, the arylene diamine compounds described in U.S. Pat. No. 4,552,834, and the like.

These compounds have -A-(TI)A in the formula (Y) at the substitutable heteroatom contained in the molecule.
-(B (Tri,,)-- is a preferred example.

The group represented by 2 is more preferably represented by the following formula (Z-
1), (Z-2), (Z-3), (Z-4) or (Z
−5).

-Formula (Z-1) -3-L, -(X,).

In the general formula (Z-1), a is an integer of 1 to 4, Ll is a + monovalent linear or branched alkylene group having 1 to 8 carbon atoms, X□ is a hydroxyl group, a carboxyl group, Cyano group, amino group having 0 to 10 carbon atoms (e.g. amino, methylamino, ethylamino, dimethylamino)
, diethyl-acuno, diisopropylamino, pyrrolidino, piperidino, morpholino, hydroxyamino), acyl groups having 1 to 10 carbon atoms (e.g. formyl, acetyl), carbamoyl groups having 1 to 10 carbon atoms (e.g. carbamoyl, dimethylcarbamoyl) , hydroxycarbamoyl, morpholinocarbonyl), WIN number of children 1 to 10
sulfonyl groups (e.g. methylsulfonyl, ethylsulfonyl), sulfamoyl groups of carbon atoms aO to lO (
For example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, pyrrolidinosulfonyl), carbonamide groups having 1 to 10 carbon atoms (for example, formamide,
acetamide), ammoniayl group having 3 to 12 carbon atoms (e.g. trimethylammonillamyl, pyridinylamyl), ureido group having 1 to 10 carbon atoms (e.g. ureido, 3-methylureido), sulfamoyl group having 0 to 10 carbon atoms Amino group (e.g. sulfamoyl group), 3,
3-dimethylsulfamoylamino), carbon number 1 -
6 represents an alkoxy group (e.g. methoxy), amidino group, guazinino group, or amidinothio group, respectively, provided that when a is plural, the plural X's may be the same or different, and is a cycloalkylene group Specific examples include methylene, ethylene, trimethylene,
ethylidene, isopropylidene, propylene, l, 2.
Examples include 3-propanetriyl.

General formula (Z-2) In general formula (Z-2), b is an integer from 1 to 6, and C is 0.
An integer of ~7, L, and is a linear or branched alkylene group having 1 to 3 carbon atoms, X, and
Y has the same meaning as Xt in formula (Z-1), and -
o--s--5o--C○o--oco--ocoo- (However, R and Rg are hydrogen atoms or carbon atoms of 1 to
10 alkyl groups (representing, for example, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxyethyl, carboxymethyl, carboxyethyl, propyl, etc.)
, respectively, but when b is multiple, multiple Y+
-Li may be the same or different (however, not all Yl is -3-) Also, when C is other than 0, X2 is Can be replaced.

General formula (Z-3) In general formula (Z-3), b%c, Lx, Ls, Xt
and X, - in formula (Z-2), c, Lx, L
Same meaning as s, Xt and Xt respectively, W is -o--
s--oco-O3O! where R represents --0SO--N- or Rco-W, -L4-N-, respectively.

R3 has the same meaning as R1 in formula (Z-2), L4 has the same meaning as beam, W has the same meaning as -0--oco--oso,
-=〇S○- or -N- respectively, and when b is plural, 3 plural S -L 2 may be the same or different, C
When is other than 0, X can be replaced with any of W, t, Z, and ri, if substitutable. However, W is −
When S-, b is never 1.

General formula (Z-4) In the general formula (Z-4), WSX and X2 have the same meaning as W, X, and X2 in the general formula (Z-3), d is an integer from O to 6, and L4 and Ls is a linking group having a total of 1 to 16 carbon atoms (for example, alkylene or 10--S--
Each represents an alkylene bonded to each other through N-. However, R4 has the same meaning as R1 in general formula (Z-2), and d is O
Otherwise, if X2 can be replaced, it can be replaced with W1L4 and .

-Format (Z-5) -S-Li -(N3).

- In the form (Z-5), is a cyclohexane group having 3 to 12 carbon atoms (e.g. cyclopropane, cyclobutane, cyclopentane, methylcyclopenkune, cyclohexane, cyclopentanone, cyclohexanone, bicyclo(2,2, 1) groups derived from pentane etc.), arylene groups having 6 to 10 carbon atoms (e.g. phenylene,
naphthylene), unsaturated heterocyclic groups having 1-10 carbon atoms (
For example, pyrrole, pyrazole, imidazole, 1.2.
3-) Riazole, 1,2.4-) Riazole, tetrazole, oxazole, thiazole, indole, indazole, benzimidazole, benzoxazole,
Benzothiazole, 1.3.4-oxadiazole, 1
, 3.4-thiadiazole, purine, tetraazaindene, isoxazole, isothiazole, pyridine, pyrimidine, pyridazine, 1,3.5-) riazine, quinoline, furan, thiophene, etc.) or number of carbon atoms 2 to 10 optionally partially saturated saturated heterocyclic groups (e.g. oxirane, thiirane, aziridine,
represents a group derived from oxetane, oxolane, thiolane, thiecune, oxane, thiane, dithione, dioxane, piperidine, morpholine, piperazine, ikudacylidine, pyrrolidine, pyrazoline, pyrazolidine, imidacilline, pyran, thiopyran, oxazoline, sulfolane, etc. .

In general formula (Z-5), X represents a hydrophilic substituent, preferably a substituent having a π substituent constant of 0.5 or less, more preferably a negative value. What is the π substituent constant?
ts for CorrelationAnalysis
s in Chemistry and Biolog
y), C. Hansch and A. Leo, John Wiley.
0, which is a value calculated for X by the method described in Wiley), 1979. The π substituent constant is shown in parentheses.

-CONTo (-1,49), -COJ (-0,3
2), -COCHi (-0,55), -NHCOCT
o (-0,97), -CHzCH*C0zH(-0,
29), -5cHzcoH(-0,31), -C1hCO□H(-0,72), -OH(-0,67), -CHzOH(-t,03), -CN(-0,57 )
, -C1(z(II (-0,57), -C)lJHg
(-1,04), -NH, (-1,23), -NHCHO (-0,98), -NHCONHz (-
1,30), -NHCHs (-0,47), -NII
SO□CH3 (-1,18), -5o3- (-4,7
6), 10CH3(-0,02), 10SO□C)! 3 (-0,88), -5O,N11
! (-1,82), -0C1hCONHz (I,37), -CNHOH(
-1,87).

- In format (Z-5), e is O to 5, preferably 1 to 3
represents an integer.

Examples of the group represented by the -M formula (Z-1) are shown below.

-3CHiCH＊CO□H1 -5CHtCHCHzOH.

OH -5GHzC82NHz.

-3CIbCHJHCHs, -5CHZC1 (JH5OtGHz, -3CIbCHxNHCOOCHs, -5CH*C)ItOH.

-5CfhCHzS (hNHx, -5(CL)3COOH.

CH3 13CHCOOH.

-3C)lICII2SO3K.

-II Examples of the group represented by formula (Z-2) are shown below.

-0CHZCHZSCHzCHZOH.

-5CHzCHzSCHzCHiCOOH1SCHzC
HzOC1(tcHtOH.

-3CHiCHtOCHxC)IzOH.

-5CHZCONHCH寞C0OH.

-5CHzCHJ(CHzCOOl() x, -i formula(
Examples of the group represented by Z-3) are shown below.

-NH(CHzCHtShCHgCHzOH.

-5(CHxC)Its)zcHzcHzOH.

HI Ha -3CH□CHtSCH2CHC)IzSGHzCHs
.

0)1 General formula (Z-4) Below are examples of groups represented by show.

10CRICHtSSCHzCToOH.

-NHC)I*CLSSC)IzC)IztlL.

NH! Hz CH3 -OCHtCLSSCLCLCOOL -3C) IzCHxSSCHzCH寞01(.

-Format (Z-5) Below are examples of groups represented by show.

C3zco□H CHiCHzOH N) It -a from a in the group represented by formula (Z-5).

is preferably a heterocyclic group. In the compound represented by the 1°-form (Y), a Buller residue is preferable to 1, and it is preferable not to use T + , T z and B4, Z is general formula (Z-1), (Z-4),
and (Z-5) are preferable, and (Z-1)
A group represented by is more preferred.

Next, specific examples of the bleach accelerator-releasing compound used in the present invention will be shown.

(B-1) (B-2) (B-3) (B-6) (B-7) 0H (B-8) H (B-9) H (B-10) CB-11) H (B-12) (B-13) (B-14) (B-15) (B-16) N.H.

(B-17) Of( (B-18) (B-19) CHxCIhSCHtCHCHtOH H (B-20) H ClbCOtH (B-22) CB-24) 1l (B-25) (B-26) l (B- 28) (B-29) (B-30) CsH+ + (t) (B-32) 4H9 (B-33) SCLCLCOJ (B-35) (B-37) C) 13 (B-38) (B- 39) (B-40) CH2CHIOH (B 41) SC1hCHICool (B-42) H (B-43) 0CONHCIIIC1hSCII□C) lzscLc
LOII (B-44) Of( (B-45) The bleach accelerator releasing compound used in the present invention is disclosed in, for example, JP-A-61-201247 and JP-A-62-1734.
No. 67, No. 62-247363, Patent Application No. 61-252
No. 847, No. 61-268870, No. 61-2688
No. 71, No. 61-268872, No. 62 = 4908
No. 1, No. 62-90442 and No. 62-186939
The bottom can be made by the method described in the issue.

The amount of the bleach accelerator-releasing compound of the present invention added to the photosensitive material is 1X10-'mol-1X10-'per 1rrf of the photosensitive material.
The bleach accelerator-releasing compound according to the present invention can be added to all layers of the light-sensitive material, but is preferably added to the light-sensitive emulsion layer.
Furthermore, the effect becomes more pronounced when it is added to more photosensitive emulsion layers.

The light-sensitive material of the present invention only needs to have at least one blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer provided on the support, and includes a light-sensitive silver halide emulsion layer and a non-light-sensitive layer. There are no particular restrictions on the number of layers or the order of the layers. A typical example is a silver halide photographic material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitivity i (Gl() / low-sensitivity green-sensitivity 1iJ (
GL/high-sensitivity red-sensitive layer (I7) 1)/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/
R11/RL order or BH/BL/G! l/GL/
They can be installed in the order of RL/R)I, etc.

Furthermore, as described in Japanese Patent Publication No. 55-34932, blue-sensitive N/G)I/
They can also be arranged in the order of RH/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer may be arranged in the order of /GL/RL/G)l/RH from the side farthest from the support. You can also do it.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, the layers may be arranged in the following order: low-speed emulsion N/medium-speed emulsion N/high-speed emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4.66327
No. 1, No. 4,705,744, No. 4,707,4
No. 36, JP-A-62-160448, JP-A No. 63-895
The multilayer effect donor layer (CL) described in the specification of No.
) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10ξ microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(I, December 978), pp. 22-23, “1. Emulsion preparation and
d types)” and N1118716 (I
November 979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafk
ides, Chesie eL Ph1sique
Photograph-ique+ Paul Mon
tel+ 1967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (G, F, DuffinPho
tographic Emulsion Chemises
try (Focal Press+1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikmanet al,
, Making and Coating Photo
graphic Ea+ulsion+ Focal
Press+ 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering) ,,
Vol. 14, pp. 248-257 (I970); U.S. Patent Nos. 4,434,226, 4,414.310, 4
, 433.048, 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may be made of different halogen M, or it may be a layered structure, or silver halides with different &H strengths are bonded by epitaxial bonding. Alternatively, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical P control, chemical ripening and spectral sensitization. Additives used in such processes are subject to Research Disclosure k1
7643 and Nα18716, and the relevant parts are summarized in the table below.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is not exposed to light during image +1 exposure to obtain a dye image.
These are fine silver halide grains that are not substantially developed during the development process, and are preferably not fogged in advance.

The fine-grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of the projected area) of 0°01 to 0.5 μm, and 0.01 to 0.5 μm.
．． 02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Masu Sarakou Soo (Goku ■Kan L) Nagigami 1 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 right column 12 Coating aid, pages 26-27 Page 650 right column Surfactant 13 Static Page 27 Same as above Inhibitor Also, deterioration of photographic performance due to formaldehyde gas In order to prevent
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435, No. 503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patents listed in ■-C to G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314.
No. 023, No. 4,511,649, European Patent No. 24
No. 9,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351,897, European Patent No. 73.636, US Patent No. 3,061,432, US Patent No. 3.725.067, Research Disclosure No. 24220 (I984) June), Japanese Patent Application Publication No. 6
No. 0-33552, Research Disclosure -N
i124230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573
No. 0, No. 55-118034, No. 60-185951
No. 4,500.630, U.S. Patent No. 4,540
．． No. 654, No. 4,556,630, International Publication 1v
Particularly preferred are those described in No. 088104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4.052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4,296,200, No. 2,369.9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2,895,826, No. 3,772
, No. 002, No. 3.758.308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3329,729, European Patent No. 121,365A
No. 249°453A, U.S. Patent No. 3,446,
No. 622, No. 4,333.999, No. 4,775
, No. 616, No. 4,451,559, No. 4,42
No. 7,767, No. 4,690,889, No. 4,
No. 254212, No. 4,296.199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are Research Disclosure No.

Section ■-G of 17643, U.S. Patent No. 4,163.670
No. 57-39413, U.S. Patent No. 4,00
Preferred are those described in No. 4,929, No. 4,138,258, and British Patent No. 1146,368. Also,
U.S. Pat. No. 4,774,181 describes a coupler that corrects unnecessary absorption of a coloring dye using a fluorescent dye released during coupling, and U.S. Pat. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming .

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, No. 570, European Patent No. 96,570, and West German Patent No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release a photographically useful rA group upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors include the previously described RD 1764
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4,248.962, U.S. Patent No. 4,782,012
Preferably, those listed in No.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131,188, JP 59-157638
No. 59-170840 is preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , multiweight couplers described in JP-A No. 4,310,618, etc., DIR redox compound releasing couplers, DIR coupler-releasing couplers, described in JP-A-60-185950, JP-A-62-24252, etc.
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
No. 02A, 313.308A, couplers that release dyes that fade after separation as described in U.S. Pat. No. 4,553i.
Ligand releasing coupler described in No. 477 etc., JP-A-63
Couplers that release leuco dyes as described in US Pat. No. 4,774,181 and couplers that release fluorescent dyes as described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl ) phthalate, bis(2,4-di-amyl phenyl) isophthalate, bis(I,1-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate etc.>, Amide 1! (N, N
-diethyldodecaneamide, N,N diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
, 4-di-tar t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N,N-dibutyl 2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 500°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

The process and effects of the latex dispersion method and specific examples of latex for impregnation are described in U.S. Pat. (ots) No. 2,541,274 and No. 2541.230.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

The present invention can be applied to a variety of photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of k 17643, and k 18716
It is described from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly 16 μm or less. Preferably, the membrane swelling rate Tl/l is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
It means the film thickness measured in days), and the film swelling rate TI/! teeth,
It can be measured according to techniques known in the art. For example, Knee Green (I, Green)
Photographic Science and Engineering (Photogr, Sci, Eng,)
It can be measured by using a swellometer (swelling membrane) of the type described in , 19@, No. 2, pp. 124-129, and Tl/z is reached when treated with a color developer for 23 minutes and 15 seconds at 30°C. The saturated film thickness is defined as 90% of the maximum swollen film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate 71/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film W-)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and the same Na 1
Development processing can be carried out by the usual methods described in the left column to right column of 615 of B716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenesia compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, -Methyl-4-AwaranoN-Ethyl-N-
β-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonic acid ξ-doethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, hendithiazoles or Mercap F compounds. In addition, if necessary, hydroxylagon, diethylhydroxylamine, sulfite, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfone Mi, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , ■-Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, alkylphosphonic acids,
Various acidifying agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxy, ethylidene- 1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,ll,N-tetramethylenephosphonic acid, ethylenecyagondi(O-hydroxyphenylacetic acid) and salts thereof can be cited as a representative example.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virapritones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pl of these color developing solutions and black and white developing solutions is 9 to 12
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 0d or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably o, ooi to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it in all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (Ill), peracids, quinones, nitro compounds, etc. Typical bleaching agents include iron (III) compounds, etc.
ta salts, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or citric acid, tartaric acid, malic acid, etc. Complex salts of , etc. can be used. Among these, ethylenediaminetetraacetic acid iron(m)tit salt and a[noboricarboxylic acid iron(III) complex salt, including 1,3-cyaminopropanetetraacetic acid iron(III) complex salt, are suitable for rapid processing and prevention of environmental pollution. preferred from the viewpoint of Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (III) t! p of bleach or bleach-fix solution using salt
H is usually 4.0 to 8, but processing can be performed at an even lower pH for speeding up the processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in Research Disclosure No. 17129 (July 1978), etc.; Thiazolidine derivatives described in Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735, U.S. Patent No. 3,706,56
Thiourea derivatives described in No. 1; West German Patent No. 1,127,
No. 715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748.43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-42.434, No. 49-59.644, No. 53
-94,927, 54-35,727, 55-
Compounds described in No. 26.506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85
No. 8, West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-
Preferred are the compounds described in US Pat. No. 95,630, and also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461, and the method of JP-A-62-183461. A method of increasing the stirring effect using a rotating means, and a method of further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. , a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved stirring speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. It is highly effective in preventing performance deterioration of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision Engineers Volume 64, P, 24
8-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Isothiazolone compounds and cyabendazole compounds, chlorinated disinfectants such as chlorinated sodium incyanurate, and other benzotriazoles, etc., described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents," (I986) Sankyo Publishing, Hygiene Technology Full volume “Microbial sterilization, sterilization, and anti-mold technology J (I982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Agents (
It is also possible to use the fungicides described in I986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of dye stabilizers that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetratin, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3.342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include the urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 1-phenyl-3-
It is also possible to incorporate birapritons.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547, No. 58-115438, etc.

The various processing solutions used in the present invention are used at a temperature of 10'C to 50"C. Normally, the temperature is 33°C to 38°C, but higher temperatures can be used to accelerate the processing and shorten the processing time. Or, conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.

(Example) The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material having the composition shown below, was prepared.

The coating amount of the photosensitive layer is expressed in g/rrr for silver halide and colloidal silver, and the amount expressed in g/rd for coupler additives and gelatin. Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer.

1st layer (Haley silane prevention layer) Black colloidal silver 0.2 gelatin
1. 3ExM-90,06 UV-10,03 UV-20,06 UV-30,06 Solv-10,15 Solv-20,15 Solv-30,05 2nd JIl (intermediate layer) Gelatin 1. 0UV-10
,03 ExC-40,02 ExF-10,004 Solv-10,l 5olv-20,1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag+4 mol%, uniform-Agl type, sphere equivalent) Diameter 0.5μ, coefficient of variation 20%, plate-shaped particles, diameter/thickness 3
, 0) Coating iI amount 1.2 Silver iodobromide emulsion (Ag 13 mol%, uniform-Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation 15%, spherical particles, diameter/thickness 1
．． 0) Coated silver amount 0.6 Gelatin 1.0ExS-14
X10-' ExS-24 Silver bromide emulsion (Ag+6 mol%, internal high Agl type with core-shell ratio 1:1, equivalent sphere diameter 0.7μ, coefficient of variation 15%)
, plate-shaped particles, diameter/r¥-mi5,0) Coating amount
0.7 1.0 3X10-'2.3X10-' 0, 15 0, 05 0, 05 0, 05 Gelatin xS-I xS-2 ExC-7 ExC-4 Solv-I Solv-3 511th (Intermediate N ) Gelatin pd-1 0,5 0,1 Solv-10,05 6th layer (low-sensitivity green-sensitive emulsion N) Silver iodobromide emulsion (Ag+4 mol%, internal high Agl type with core-shell ratio of 1:1, equivalent to sphere) Diameter 0.5μ, coefficient of variation 15%,
Plate-shaped particles, diameter/thickness 4.0) Coated silver amount 0.3
5 Silver iodobromide emulsion (Ag 13 mol%, uniform, 6.gl type, equivalent sphere diameter 0.3 μ, coefficient of variation 25%, spherical grains, diameter/W
- Mi 1.0) Coated silver amount 0.20 Gelatin 1.0ExS-35
X10-'ExS-43xio-'ExS-5txto-' ExM-80,4 ExM-90,01 ExM-100,02 ExY-110,03 Solv-10,3 Solv-40,05 7th layer (high sensitivity green Sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, internal high Agl type with core-shell ratio 1:3, equivalent sphere diameter 0.7μ, coefficient of variation 20%,
Plate-shaped particles, diameter/W-view 5.0) Coated silver amount 0.
8 0.5 5X10-'3X10-'lXl0-' 0.1 0.02 0.03 0.03 0.04 0.2 0.01 Gelatin ExS -3 ExS-4 ExS-5 xM-6 xM-9 ExY-11 BxC-2 xM-14 Solv-I Solv-4 No. 8N (middle N) Gelatin pd-I Solv-1 0,5 0,05 0,02 No. 971 (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, internal high Agl type with core-to-shell ratio 11, equivalent sphere diameter 1.0 μ, coefficient of variation 15%, plate-like grains, diameter/thickness 6.0) Coated lI amount 0.35 Silver iodobromide emulsion (Ag 12 mol%, internal high AgI type with core-shell ratio l:1, equivalent sphere diameter 0.4μ, coefficient of variation 20%,
Plate-shaped particles, diameter/thickness 6.0) Coated silver amount 0.2
0 gelatin 0. 5ExS-3
8XlO-' ExY-110,11 ExM-120,03 ExM-140,10 Solv-10,20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0. 5Cpd-20,13 Solv-10,13 Cpd-10,10 11th Jilil (Low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform Agl type, equivalent sphere diameter 0.7
μ, coefficient of variation 15%, plate-like grains, diameter/thickness 7.0) Coated silver I O03 Silver iodobromide emulsion (Ag 13 mol%, uniform-Agl type, equivalent sphere diameter 0.3μ, coefficient of variation 25%, plate shaped particles, diameter/thickness 7
．． 0) Coated silver amount 0.15 Gelatin 1. 6ExS-6
'2X10-'ExC-16
0,05 ExC-20,10 BxC-30,02 ExY-130,07 ExY-151,0 Solv-10,20 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgIIO mol%, internal High Agl type, equivalent sphere diameter 1.0μ, coefficient of variation 25%, multi-twin plate-like particles,
Diameter/thickness 280) Coated silver amount 0.5 Gelatin 0. 5ExS-6
1X 10-' ExY-150,20 ExY-130,01 Solv-10,10 13th layer (first protective layer) Gelatin 0. 8UV-40
- l UV-50,15 Solv-10,01 Solv-20,01 14th layer (second protective layer) Fine grain silver bromide emulsion (Ag 12 mol %, uniform Agl type, equivalent sphere diameter 0.07μ) 0. 5 Gelatin 0.45 Polymethyl methacrylate particle diameter 1.5μ 0. 2H1O,4 Cpd-50,5 Cpd-60,5 Cpd-80,2 In addition to the above components, each layer contains emulsion stabilizer Cpd-3 (
0.04g/po) Surfactant cP d-4 (0.02g
/rrf) was added as a coating aid.

V-1 V-1 V-4 V-5 olv-1 tricresyl phosphate olv-2 dibutyl phthalate pd pd-2 pd-7 CiH+s pd-3 pd-4 cP a-s Nil industry ExC-1 ExC-2 ExC-3 bull chapter tliLU=shiN3 xC-4 ExC-8 ExC-5 ExC-7 已xM-8 xM-9 ExM-6 ExY-11 ExM-12 ExM-13 ExY-14 ExY-15 xC-16 xS ExS-2 ExS-3 ExS-4 ExS-5 ExS-6 -1 Cut"CH-3Os CHt C0NHCL
C1l1tsuboCHSow CHI C0NH-C
LxF-1 Preparation of Sample 102 In Sample 101, the yellow colloidal silver added to the 10th layer was removed, and instead Comparative Compound A was dissolved in an equal weight of high boiling point solvent HBS-2, and a surfactant was added. It was prepared in the same manner as the sample lot except that after mixing with gelatin solution, it was emulsified and dispersed using a homogenizer and added (0.25 g/rrf).

Preparation of Sample 103 In Sample 102, dispersion S-1 of the present invention was added in place of Comparative Compound A added to the 10th layer, and the amount of l-25 added was 0.
．． It was produced in the same manner as Sample 102 except that it was added so that the amount was 22 g/rrf.

Preparation of sample 104 In sample 103, use 32 instead of dispersion S-1! −
28(7) Addition amount, /)<0. 24 g/rd nits
Sample 103 was prepared in the same manner as sample 103, except that the sample was added in the same manner as sample 103.

Preparation of samples 105-10B In samples 101-104, cyan coupler E of the fourth layer
Samples 101 to 104 were prepared in the same manner as Samples 101 to 104, except that XC-7 was replaced with coupler B-8 of the present invention in equal molar amounts.

Preparation of samples 109 to 112 In samples 105 to 108, the 7th N coupler EXM-
Samples 105 to 108 were prepared in the same manner as samples 105 to 108, except that coupler B-25 of the present invention was used in place of coupler B-25 of the present invention in an equimolar amount.

Preparation of Samples 113 to 116 In Samples 101 to 104, dye dispersion S-3 of the present invention was added to I[[-3
Samples 101 to 104 were prepared in the same manner as Samples 101 to 104, except that the total amount of Samples 1 and 1-12 was 0.23 g/rd.

Preparation of samples 117-120 In samples 113-116, the 4th J! , the seventh layer couplers EXC-7 and EXM-6 are B-8 and B-25, respectively.
Samples 113 to 116 were prepared in the same manner as Samples 113 to 116, except that the same molar ratio was changed.

Fine powder dye dispersion S-t! J1! ! ! Method: The dye was dispersed in a vibrating ball mill according to the following method.

Water (21.7d) and 3-15% aqueous solution of p-octylphenoxypoly (degree of polymerization 10) oxyethylene ether 0.5 g were placed in a 700-bot mill, Dye of the present invention (I-25)1. OOg and 500 zirconium oxide beads (diameter 1 m) were added and the contents were dispersed for 2 hours. The vibrating ball mill used was a BO type manufactured by Chuo Kakoki Department.

The contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were filtered to obtain a dye gelatin dispersion.

S-2 (dye 1-28), 5-3 (dye 111-3/IIl[-12 (weight ratio 1:1)
) was prepared.

Comparative Compound A (compound described in JP-A No. 62-32460) Samples 101 to 120 obtained by the above method were exposed with a step wedge and then treated with the following processing steps (resin). Minimum density of the treated sample The yellow density of 40CM was measured.
The amount of residual silver in the portion exposed to S was measured using fluorescent X-rays.

The results are shown in Table 1.

As is clear from Table 1, the amount of residual silver in the samples prepared by the combination of the present invention was significantly lower than when each was used alone.
It can be seen that they act synergistically. Furthermore, when both the colloidal silver for the antihalation silane and the colloidal silver for the yellow filter are replaced with the dye of the present invention, the effect is quite remarkable.

The minimum concentration was also lower than that of the sample containing Comparative Compound A, indicating that the decolorizing property was sufficient.

Processing process (replenishment amount: per meter length of 35m wide photosensitive material (color developer) Hydroxylthyliminodiacetic acid Sodium sulfite Potassium carbonate Potassium iodide Hydroxylamine sulfate 4 (N-ethyl-N-β) -Hydroxyethyl acetate) - Add 2-methylaniline sulfate solution to pH (bleaching solution) 1.3-diaminopropanetetraacetic acid ferric complex salt mother solution 5° (g) Replenisher solution (g) 6.0 5. 0 37,0 0.5 3.6 1゜0XIO-''mol 1゜3X10-''mol 1,01 10.00 Mother liquor (g) 30 1,01 10.15 Replenisher (g) 90 1,3-diamino Add propanetetraacetic acid ammonium bromide acetic acid ammonium nitrate aqueous solution and HJM with acetic acid and ammonia (fixing solution) 700g/z) Rodan ammonium 3, 0 5 0 0 1, 01 pH 4,3 Mother liquor (g) 5.0 0゜ 5 10, 0 8, 0 4, 0 20 0 0 1, 01 pH 3,5 Replenisher (g) ) 7,0 0.7 12,0 10,0 170゜W1 200゜〇- 100゜150゜thiourea 3.0 3.6-dithia-1,3゜0 8-octanediol Add water 1 .01 Add ammonium acetate 6,5 to pH (Stable solution) Mother solution, replenisher Common formalin (37%) 5-chloro-2-methyl-4-isothiazolin-3-one 2-methyl-4-isothiazolin-3-one Surfactant 5.0 5, 0 1, OA 6.7 ■, 2- 6, 0■ 3゜0-■ 0゜ Add ethylene glycol water to pH 1, 0 1, 01 5, O-7,0 Example 2 Sample 201 was prepared by coating an emulsion layer having the composition shown below on an undercoated cellulose triacetate support.

1st layer: anti-halation layer black colloidal silver-1-2 1l-1 gelatin 2nd layer: intermediate layer pd-D f 1-3 gelatin 3rd layer: intermediate layer covered with fine-grain silver iodobromide emulsion (average Particle size 0.06μ, Agl content 1 mol%) iI amount 0, 25g/n (0.1g/n? 0.1g/rJ 0.1cc/n? 1, 9g/rd 10■/d 40rrg/rd 0 .4g/rd 0, 05g/n? Gelatin 0.4g/m 4th layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain Monodispersed cubes with a diameter of 064μ and an Agl content of 4.5 mol%, and an average particle size of 0°3μ and an Agl content of 4.5 mol%.
Silver content 0.46/cd Coupler C-10.2 g/rd C-20.05 g/rl Oil 1 0.
lee/rrr gelatin 0.8
g/m 5th N: Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse cubic with an average grain size of 0.5 μm and an Agl content of 4 mol%) ) Ginji 0. 4g/rd Coupler C-10,2g/n (C-30,2g/n(C-20,05g/m Of 1-1 0. Ice/m
Gelatin 0.8g/rd 6th P
i: Third red light emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse twin grains with average grain size 0.7 μm and Agl content 2 mol%) Silver Amount 0.4g/rd Coupler C-30.7g/nr Coupler B-10.3g/rd Gelatin 1.1g/rrr No. 7
Layer: Interlayer dye D-l 0.02g/m gelatin 0.6g/r+7 8th J! :
Silver iodobromide emulsion covered with an intermediate layer (average grain size 0.06, um, A
gl content 0.3 mol%) Compound Cpd-A o, 2g1m gelatin 1.0g/rd 9th layer:
First green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.4μ, Agl content 4.5 mol%, monodisperse cubic and average grain size 0゜2μ, Agl content 4.5 mol%
(a one-to-one mixture of monodisperse cubes) Silver amount 0.5 g/n? Coupler C-40, 10g/rd Coupler C-70, Log/rd Coupler C-80, Log/rrr Compound Cpd-B O, Q3g/mCpd
-E 0. 1g/rdCpd-F
0. 1g/dCpd-Cr
o, 05g/n (Cpd-H0,05g/pogelatin 0.5g/rrr 1st
Layer 0: 2nd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (monodisperse cubic with average diameter 0.5 μm and Agl content 3 mol%) Silver amount 0.4 g /r+? Coupler C-40, 10g/n (Coupler C-70, log/n? Coupler C-80, 10g/rrr Compound Cpd-80, 03g/rd Cpd-E O,Lg/rdCpd
-FO,Ig//cpd-c
o, 05g/rrlCpd-H0,05g/
m Gelatin 0.6g/rrr 1st
1st layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (average grain size in terms of spheres 0.6μ, Agl content 1096μ, diameter/
Monodisperse flat plate with an average thickness of 7) Coupler C-4 Coupler C-7 Coupler C-8 Compound Cpd-B Cpd-E Cpd-F Cpd-G Silver amount o, 5g/rrr O,4g/m 0, 2g/rrr 0.2g/n? 0.08g/resistance 0, 1g/n? 0, 1g/m O,Ig/r&Cpd-)f O,Lg/Igelatin L,Og/cd 12th layer dye D-20,05g/rd Gelatin Q, 6g/m 13th layer: Yellow filter layer Yellow colloid Silver 0. Lglrd Compound Cpd-A 0101g7m Gelatin
1.1g/m 14th layer: Intermediate layer gelatin 0. 6g/m 15th
Layer: First blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (average grain size 0.4μ, Agl content 3 mol%, monodisperse cubic and average grain size 0.2μ) , a 1:1 mixture of monodisperse cubes with an Agl content of 3 mol %) i amount 0. 6gZrd Coupler C-50, 6g/rrr Gelatin 0.8g/rrF 1st
6th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (average grain size 0.5 μm, monodispersed cubes with Ag 1812 mol%) i 艮 ii 0.4 Fin / d Coupler〇-50, 3g/rd C-60, 3g/n? Gelatin 0. 9g/rrr 17th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-S and S-6 (average grain size in terms of spheres 0.7μ, AgI content 1.5 mol%, A flat plate with an average diameter/thickness of 7) Silver! 0.4g/rd Ka coupler C-60, 7g/m Gelatin 1.2 g/m No. 18
Layer: first protective layer u-10,04g/rrr u-30,03g/rrr U-4-0,03g/rd U-50,05g/m u-6o,o5 g/' Compound Cpd-CO, ,8g/n? Dye D-30.05g/n (gelatin 0.1g1rd No. 19
N: Silver iodobromide emulsion covered with a second protective layer (average grain size 0.06 μm s
A g I content 1 mol%) Silver amount 0.1 g/n (0.4 g 1rd Gelatin 2nd ON: 3rd protective layer polymethyl methacrylate (average particle size 1.5 μm) 4=6 copolymer of methyl methacrylate and acrylic acid Coalescence (average particle size 1.5μm) O, Ig/rrf silicone oil 0.03g/rrrw-1
3g/rrf Gelatin 0.4g/rrr In addition to the above composition, gelatin hardener H0, 1g/rr is added to each layer.
rr-l and surfactant were added.

-1 H -2 H -3 H -4 -5 -6 C-7 Coupler C-8 Oi 1-1 Dibutyl phthalate 11-2 Tricresyl phosphate pd-A H pa-B pti-c pd-E Cpd- G Cpd-H Cpd-D H -1 #I+9 (sec) -2 -3 -4 -5 -6- -2 -3 -4 zHs -5 ZHS SO38N (CtH,)3 S-6 D-'L -2 -3 -1 CHylICR5OzCHzCONHCHiCHt-C
H5OtCHzCONHCHx-1 CI.

Preparation of Sample 202 In Sample 201, the first layer of black colloidal silver was removed, and instead, dye dispersion S-3 used in Example 1 of the present invention was added.
-3 and I[[-12 total addition amount is 0.24g/rr
It was produced in the same manner as Sample 201 except that the addition was made so that r was added.

Preparation of sample 203 Compound B of the present invention in sample 201 odor-C1 3rd FJ-
420.2g/rr? was emulsified and dispersed in an equal amount of Of +-1. Other than that, it was produced in the same manner as Sample 201.

Preparation of sample 204 In sample 202, B- used in sample 203 was added to the third layer.
Sample 202 was prepared in the same manner as Sample 202 except that the same amount of the dispersion of Sample 202 was added.

Preparation of Samples 205 to 208 In Samples 201 to 204, yellow colloidal silver of No. 13 Fi was removed, and instead, dispersion S of Compound 1-25 of the present invention was used.
-1! Samples 201 to 204 were prepared in the same manner as Samples 201 to 204, except that -25 was coated in an amount of 0.21 g/cd.

The obtained samples 201 to 208 were passed through a gradation wedge 2
A white rice exposure of 0 CMS was applied, and the following development process was performed.

Maximum exposure il (20CMS) of the obtained developed sample
The amount of residual silver in each sample was measured using fluorescent X-rays.

The results are shown in Table 2.

As is clear from Table 2, desilvering performance is improved by removing colloidal silver and replacing it with dye, but when combined with the desilvering accelerator releasing compound of the present invention, the amount of residual silver is significantly reduced. It can be seen that

Processing process Time Temperature - Development 6 minutes Washing with water at 38℃
2 minutes inversion 2 minutes Color development 6 minutes Adjustment
1 minute Bleach
Set for 3 minutes Wash with water for 3 minutes Stabilize for 4 minutes 1 minute Dry at room temperature
The composition of the drying solution used is as follows.

Tamanili East Liquid Water 700
dNitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2
gSodium sulfite 20g Hydroquinone monosulfonate
30g sodium carbonate (-water salt)
30g1-phenyl-4methyl-4-hydrofukimethyl-3pyrazolidone
2 g potassium bromide
2.5g potassium thiocyanate 1
．． 2g potassium iodide (0.1% solution) 2-
Add water for 1000d
-Liquid.

Water nitrilo-N, N, N-) rimethylenephosphonic acid pentasodium salt stannous chloride (trihydrate salt) p-aminophenol sodium hydroxide Add glacial acetic acid water and standing satobean liquid water nitrilo-N, N, N-) Rimethylenephosphonic acid pentasodium salt Sodium sulfite Sodium triphosphate (I2 hydrate) Potassium bromide Potassium iodide (0.1% solution) Sodium hydroxide Citrazate N-Ethyl-N- (β-methane 70 〇- g g 0.1g g 5- 1000d 00d g g 6g g 01R1 g 1, 5g sulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 3.6-dithiaoctane-1° 8- Add diol water and make shellfish - straight water Sodium sulfite Sodium ethylenediamine tetraester (trihydrate) Add thioglycerin glacial acetic acid water and make star - Soybean liquid Water Ethylenediamine sodium tetraphosphate (trihydrate) Ethylenediamine tetra Section 6i Iron (I [[) Ammonium (
Trihydrate) 1g g 1, OOOd 70〇- 2g g 0, 4- 1000d 001d 20g Add potassium bromide water and make it constant - Toyoichiso water Sodium thiosulfate Sodium bisulfite water and make it constant Strict water formalin (37% by weight) Fuji Drywell (Fuji Film special surfactant) Add water 00g 1 00 0d 00- 80.0g 5, 0g 5, 0g 000d 80 〇- 5, 0d 5, 0- 000m ( Effects of the Invention) It can be seen that according to the present invention, a color photographic material with excellent desilvering properties can be obtained. Moreover, the above-mentioned characteristics can also be obtained through a rapid development process, and the practical merits of the present invention are extremely large.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the light-sensitive material contains at least one compound selected from the following general formulas (I) to (V). A silver halide color having a hydrophilic colloid layer containing a microcrystalline dispersion of seeds, and containing at least one bleach accelerator-releasing compound represented by the following general formula (Y) in at least one layer. Photographic material. General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A and A' may be the same or different, and are carboxyphenyl group, sulfamoylphenyl represents a substituted or unsubstituted acidic nucleus having a group, a sulfonamidophenyl group, a carboxyalkyl group, or a hydroxyphenyl group, and examples of the acidic nucleus include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4- selected from the group consisting of oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indanedione, pyrazolopyridine and hydroxypyridone. B is a substituted or unsubstituted basic nucleus having a carboxyl group, sulfamoyl group or sulfonamide group; The basic nucleus is selected from the group consisting of pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole, and pyrrole.R represents a hydrogen atom or an alkyl group, and R_1 and R_2 are each substituted or unsubstituted. represents an alkyl group, substituted or unsubstituted aryl group, acyl group or sulfonyl group, R
_1 and R_2 may be connected to form a 5- or 6-membered ring. R_3 and R_4 represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, or a halogen atom, and R_4 and R_5 each represent a hydrogen atom or R_1 and R
Represents a group of nonmetallic atoms necessary for _4 or R_2 and R_5 to connect to form a 5- or 6-membered ring. L_1, L_2, L_3 each represent a substituted or unsubstituted methine group, X, Y each represent an electron-withdrawing group,
Either X or Y has at least one carboxyphenyl group, sulfamoylphenyl group, sulfonamidophenyl group, carboxyalkyl group, or hydroxyphenyl group, m represents 0 or 1, and n represents 0 or 1 Or represents 2. p represents 0 or 1, but when p is 0, R_3
represents a hydroxy group or a carboxy group, and R_4 and R_5 represent a hydrogen atom. ) General formula (Y) A-(T_1)_l-[B-(T_2)_n]_m-Z
(In the formula, A is a group whose bond with (T_1)_l or less is cleaved by reaction with the oxidized product of an aromatic primary amine developer, T
_1 and T_2 are timing groups, B is (T_1)_l
After the bond with the above is cleaved, the bond with (T_2)_n or less is cleaved by reaction with the oxidized product of the aromatic primary amine developer, and Z is the group with [B-(T_2)_n]_m or more. l, m and n each represent an integer of 0 or 1;